Pesticidal compositions containing phosphoric esters and divalent sulphur compounds

ABSTRACT

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

United States Patent U.S. Cl. 424-175 8 Claims ABSTRACT OF THEDISCLQSURE Pesticidal composition comprising: a pesticidal, phosphoricester the molecule of which has at least one alkyl group of 1 to 3carbon atoms, 0.05 to 10% of an agent stabilising the said ester againstdecomposition by protonisation, together with adjuvants characterised inthat the stabilising agent comprises at least one sulphur compoundcontaining per molecule at least one divalent sulphur atom of which onevalence is bonded to an atom chosen from sulphur, carbon, nitrogen,hydrogen, and metals capable of giving a salt, the other valence beingbonded to an atom chosen from hydrogen, the carbon atom already noted, asecond carbon atom, the nitrogen atom already noted, a second nitrogenatom, the metal atom already noted in the case of a metal of valencegreater than one, a second atom of metal and oxygen when the firstvalence is not attached to an atom of hydrogen, the proportion ofsulphur calculated with reference to the weight of the sulphur compoundbeing between 5 and 99%. Process for stabilising a phosphoric ester ofwhich the molecule possesses at least one alkyl group containing 1 to 3carbon atoms characterised in that there is added to the phosphoricester or to a mixture which contains it 0.05 to calculated on the'weight of the phosphoric acid ester of an agent capable of stabilisingthe said phosphoric ester against protonisation and comprising at leastone sulphur compound such as that defined thereupon.

This invention concerns a process for stabilising pesticidal phosphoricesters, and compositions based on phosphoric esters so stabilised.

Phosphoric esters are nowadays very widespread for pesticidal use,particularly for insecticides. Their value is due principally to speedof action and the absence of accumulation of these compounds in livingtissue as a result of their rapid hydrolysis in situ.

This latter characteristic which gives them a net advantage over the socalled chlorinated pesticides, presents however a very graveinconvenience; the sensitivity of certain phosphoric esters to humidity,even simply that of the atmosphere, is such that their decompositiontakes place without their being able to act on the pest organisms: thephosphoric esters which are sensitive are more particularly those whichcontain one or more low alkyl groups, such as methyl, ethyl, propyl orisopropyl groups attached to the phosphoric anion; this produces, oncontact with molecules of water, an at least partial decomposition" ofthese esters by protonisation, i.e. by displacement of one low alkylgroup in favour of a hydrogen atom.

Among the sensitive phosphoric esters special mention should be made ofO-2,2-dichlorovinyl-0,0-dimethylphosphate, better known under the commonname Dichlorvos and the abbreviation DDVP, the use of which in permanentinsecticidal devices known as evaporators has undergone a tremendousincrease in recent years.

Various means of stabilisation have already been suggested for limitingthe decomposition of these phosphoric esters but they are generallytoxic, for example phenols,

3,836,643 Patented Sept. 17, 1974 amines and low nitrogen heterocycles;another useful class of stabiliser comprises azoic and hydrozoniccompounds but these have a strong col-ouration power so that they cannotalways be used. The use of anhydrides or epoxides has also been used butit is known that these compounds act by fixation, either of a moleculeof Water or a molecule of free acid; it can be seen that this process islimited stoichiometrically and that the stabilisation ceases when allthe stabiliser has entered into reaction; this leads to the necessity ofusing substantial proportions of these stabilisers which is noteconomic.

The present invention has as its object the stabilisation of pesticidalphosphoric esters by using substances more efficacious than those notedabove and which do not possess the inconveniences: these substances aresulphur compounds; they are suitable in particular at relatively lowconcentrations for preserving phosphoric esters against protonisation.Thus the invention comprises pesticidal compositions comprising:

(A) 5 to 99.95%, calculated on the weight of the composition, of apesticidal, phosphoric ester the molecule of which has at least onealkyl group of 1-3 carbon atoms,

(B) 0.05 to 10%, calculated on the weight of the phosphoric ester, of anagent stabilising said ester against decomposition by protonisation,

(C) 0 to calculated on the weight of the composition, one of moresolvents for the phosphoric ester, liquid or solid under pressure orotherwise, and

(D) 0 to 50%, calculated on the weight of the composition of one or moreinert adjuvants chosen from mineral adjuvants and organic adjuvantscompatible with the phosphoric ester,

said composition being characterised in that the stabilising agentcomprises at least one sulphur compound containing per molecule at leastone divalant sulphur atom of which one valence is bonded to an atomchosen from sulphur, carbon, nitrogen, hydrogen, and a metal capable ofgiving a salt, the other valence being bonded to an atom chosen fromhydrogen, the carbon atom already noted, a second carbon atom, thenitrogen atom already noted, a second nitrogen atom, the metal atomalready noted in the case of a metal of valence greater than one, asecond atom of metal and oxygen when the first valence is not attachedto an atom of hydrogen, the proportion of sulphur calculated withreference to the weight of the sulphur compound being between 5 and 99%.

The present invention also includes a process for stabilising aphosphoric ester of which the molecule possesses at least one alkylgroup containing 1-3 carbon atoms in admixture with 0.05 to 10%calculated on the weight of the phosphoric ester, of an agentstabilising the said ester against decomposition by protonisation, 0 to90%, calculated on the weight of the composition, of one or moresolvents for the phosphoric ester which are solid or liquid underpressure or otherwise and 0 to 50%, calculated on the weight of thecomposition, of one or more inert adjuvants selected from mineraladjuvants and organic adjuvants compatible with the phosphoric ester,the said process being characterised in that there is added to thephosphoric ester or to a mixture which contains it, 0.05 to 10%calculated on the weight of the phosphoric acid ester of an agentcapable of stablising said phosphoric ester against protonisation andcomprising at least one sulphur compound such as that defined above.

The quantities of stabilising agent used according to the presentinvention are preferably between 0.05 and 4% based on the weight of thephosphoric ester.

In the sulphur compounds such as those defined accord ing to theinvention the valences of the atom of sulphur which are bonded toanother atom or to other atoms in a molecule of the sulphur compoundaccording to the invention can be constituted by a homopolar bondresulting from the displacement from a 1r electron doublet, by one ortwo heteropolar bonds resulting from an exchange of electrons betweenthe sulphur and the atom to which it is bonded or by one or twoelectrovalences resulting from electrostatic attraction between two ionsof opposite polarity.

The sulphur compounds preferred for use in the present invention are asfollows:

(1) Sulfanes defined by formula I in which n is a whole number between 1and 6; such compounds are for example:

hydrogen monosulfide hydrogen bisulfide hydrogen trisulfide hydrogentetrasulfide hydrogen pentasulfide hydrogen hexasulfide (sulphur content98.9% by weight) (2) Mercaptans defined by formula II (II) HS-R andoxygen, a second and a third ring member being chosen from the group inwhich R" is a group chosen from hydrogen, phenyl, and an alkyl orcycloalkyl group containing 1-10 carbon atoms and R' is hydrogen,phenyl, or an alkyl group containing l-4 carbon atoms.

(f) the groups (a) to (e) noted above carrying 1-3 substituents chosenfrom fluorine, chlorine and bromine and (g) the groups (a) to (e) notedabove carrying a substituent chosen from carboxy, alkoxy carbonyl,mercaptoalkoxy carbonyl containing 2 to 6 atoms of carbon and an aminogroup in which R and R" are the same or different and are chosen fromhydrogen and alkyl residues containing 1-10 atoms of carbon and (ii) agroup -ASH in which A is a group chosen from alkylene containing 213carbon atoms, phenylene, toluylene and 1,2-bis(methylene carbonyloxy)ethylene. Such compounds are for example the following:

Octadecanethiol 1,2-ethanedithiol 2-decyl-1,3-propanedithiolbutyl-2-mercapto acetate pentyl-Z-mercapto acetate benzenethiol 4-bromobenzenethiol 4-fluoro benzenethiol 4 2,4,5-trichloro benzenethiol2,4,6-tribromo benzenethiol 2-chloro propanethiol bis-mercaptoacetate ofethane-1,2-diyl methanethiol butanethiol dodecanethiol1,10-decanedithiol 1,12-dodecanedithiol benzylmercaptan1,2-butanedithi0l 1,4-butanedithiol 4-tertiobutyl benzenethiol1,3-benzenedithiol 4-chloro benzenethiol 3,4-toluenedithiol4,S-diphenyl-Z-imidazolethiol ethyl-2-mercapto acetate methyl-3-mercaptopropionate Z-mercapto benzoic acid 3-amino-5-mercapto-l,2,4-triazoleZ-amino benzenethiol Z-N-decylamino ethanethiol Z-quinoleinethiolZ-mercapto benzoxazole Z-mercapto benzimidazole 2-mercapto pyridine3-mercapto-1,2,4-triazole 2-N-N-diethylamino ethanethiolS-chloro-Z-mercapto benzimidazole 5,6-dichloro-2-mercapto benzimidazole2-mercapto-1-methyl benzimidazole l-butyl-Z-mercapto benzimidazole2-mercapto-2-phenyl bcnzimidazole Z-mercapto ethyl-2-mercaptoacetate2-mercaptopentyl-3-mercapto propionate Z-mercapto-l-methyl imidazole (3)sulfides defined by formula III: (111 b )n b in which R anh R areindependently chosen from:

(a) an alkyl of 1 to 18 carbon atoms,

(b) phenyl (c) benzyl (d) morpholinyl (e) piperidyl (g) benzothiazolyl(h) benzimidazolyl (i) benzoxazolyl (j) the groups (a) to (c) justmentioned carrying 1-3 substitutents chosen from fluorine, chlorine,bromine, hydroxy, mercapto, nitro, cyano, carboxy, alkoxy carbonyl of L5carbon atoms, and anino as defined in 2 above and an alkyl containingl-4 carbon atoms and n represents a whole number between 1 and 6.

Such compositions are, for example, the following:

2-thia hexane S-thia nonane 4-methylthio phenol4-methylthio-3-methylphenol Z-methylthio benzirnidazole Z-methylthiobenzoxazole benzylthiobenzene 4(4-amino phenylthio) nitrobenzenemethyl-3-methylthio propionate 4-methylthio-2,6-dimethylphenol1-ch1oro-2-thia propane methy1-4-thia valerianate 2-thia propyl benzenebis (4-decylamino phenyl) sulfide bis(4-djmethy1amino phenyl) sulfidebis (4-amino phenyl) sulfide bis(2,4-hydroxy phenyl) sulfide bis(2-aminophenyl) sulfide didecyl sulfide dioctadecyl sulfide didodecyl sulfidedi-4-piperidyl sulfide di-4-morpholiny1 sulfide diphenyl sulfidebis(5-chloro2-hydroxy-3-methyl phenyl) sulfide bis(4-nitro phenyl)sulfide bis(5-chloro-2-hydroxy phenyl) sulfide bis(4-amino-4-nitrophenyl) sulfide bis(3,5-dichloro-2-hydroxy phenyl) sulfide dimethyldisulfide dioctyl disulfide dibutyl disulfide bis (2-mercapto ethyl)sulfide didodecyl disulfide dioctadecyl disulfide dibenzyl disulfidebis(ethoxy carbonyl) disulfide 2,3-dithia heneicosanetrichloromethylbithiobenzene trichloromethylbi-4-thiofluorobenzenetrichloromethylbi-4-thiobromobenzene1,4,5-trichloro-2-trichloromethylbithiobenzene (2,3-dithiabutyl) benzene2-dich10rofiuoromethylbithiabenzothiazole bis(4-dimethylamino phenyl)disulfide bis (4-decylamino phenyl) disulfide bis(2-hydroxy phenyl)disulfide bis (4-chloro-2-hydroxy phenyl) disulfide 1,4-bis(pentoxycarbonyl)-2,3-dithia butane 4(4-aminophenyldithio) nitrobenzenebis(4-nitrophenyl) disulfide diphenyldisulfide bis(2-cyano phenyl)disulfide bis(2-car-boxypheny1) disulfide bis(4-amino phenyl) disulfidebis(2-amino-4-chloro phenyl) disulfide 4-dimorpholinyl disulfide4-dipiperidyl disulfide 2-dipyridyl disulfide 4-dipyridyl disulfide2-dibenzothiazolyl disulfide 1,6-dimercapto-3,4-dithia hexane1,4-dicyano-2,3-dithiabutane 1,4-dicarboxy-2,3-dithiabutane1,6-dicarboXy-3,4-dithiahexane 1,4-bis(methoxycarbonyl)-2,3-dithiabutanediphenyl trisulfide Z-dibenzothiazolyl trisulfide Z-dipyridyl trisulfidebis(4-chlorophenyl) trisulfide bis(2,4,5-trichloro phenyl) trisulfidedibutyl trisulfide dimethyl trisulfide dibenzyl trisulfide didodecyltrisulfide dioctadecyl trisulfide diisopropyl trisulfideZ-dibenzothiazolyl trisulfide Z-dipyridyl tetrasulfide dibutyltetrasulfide didodecyl tetrasulfide dioctadecyl tetrasulfide diphenyltetrasulfide Z-dibenzothiazolyl tetrasulfide ditertbutylpentasulfideditertdodecylpentasulfide bis(4-chloro phenyl) pentasulfideditertdodecylhexasulfide didecylhexasulfide dipropylhexasulfidedioctadecylhexasulfide dibenzylhexasulfide bis(4-dimethylamino phenyl)hexasulfide bis (4-nitrophenyl) hexasulfide 2-piperidinothiobenzothiazole Z-mercapto benzothiazole 2-morpholinothiobenzothiazole 3-thiaglutaric acid butyl-3-thiaglutaratemethyl-S-thiapimelate isopropyl-2,4-diethyl-3-thiaglutarate3-thiaglutaronitrile (4a) Heterocyclic compounds which comprise 5 to 23ring members forming 1 to 5 rings with at most 2 to 3 fused rings, whichcomprise 1-3 rings which each contain an S chain member and 2 otherchain members chosen from the groups the remainder of the chain membersbeing chosen from among the groupings R2 (I3R1 and \C/ II R3 theheterocyclic compounds With fused rings being chosen from among those ofWhich all the hetero chain members are contained in one and the samering, this ring being the central ring in the case of 3 fused rings, allthe ring members being chosen taking into account that all the valencesof the heterocyclic compound should be saturated, R R and R beingindependently chosen from hydrogen, chlorine, bromine, fluorine, alkylof 1-5 carbon atoms, trifiuoromethyl, nitro, and

tetrahydrothiophene Z-amino thiazoline 2-amino thiazole Z-acetamidothiazole 2-amino-4-methyl thiazole 2-acetamido-4-methyl thiazole2-amino-4-phenyl thiazole Z-amino-S-nitro thiazole Z-amino-S-chlorothiazole benzothiazole Z-methyl benzothiazole 2,5-dimethyl benzothiazole2-amino benzothiazole 7 2-amino-4-chloro benzothiazole 2-amino-6-chlorobenzothiazole Z-methylthio benzothiazole Z-methylthio benzimidazole2,5-bis(4-pyridyl)-1,3,4-thiadiazolc phenothiazine 2-chlorophenothiazine 2-trifluoromethyl phenothiazine 2-methoxy phenothiazine3-methyl-2-oxo benzothiazolidine Z-mercapto benzothiazoleS-chloro-Z-mercapto benzothiazole Z-mercapto thiazoleZ-mercapto-l,3,4-thiadiazole 2,5-dimercapto thiadiazole2-mercapto-4-phenyl-1,3,4-thiadiazole2-mercapto-4-methyl-1,3,4-thiadiazole-amino-2-mercapto-1,3,4-thiadiazole N-methyl benzothiazolethione-2N-methyl thiazolethione-2 N-methyl thiazolidinethione-2 4-buty1 N-methylthiazolinethione-Z 4-oxo-2-thioXo thiazolidine3-ethyl-4-oXo-2-thioxo-thiazolidine 3-methy1-4-oxo-S-phenylazo-Z-thioxothiazolidine 3-methyl-5 (4-nitro phenylazo)-4-oxo-2-thioxo thiazolidine5-(4-methoxy phenylazo)-4-oxo-2-thioxo thiazolidine 5- (Z-methylphenylazo)-4-oxo-2-thioxo thiazolidine 5-(2chlorophenylazo)-4-oxo-2-thioxo thiazolidine 5-(2,4-dichlorophenylazo)-4-oXo-2-thioxo thiazolidine 5- 2-chloro-4-nitro phenylazo-4-oxo-2-thioxo thiazolidine5-mercapto-3-phenyl-2-thioxo-1,3,4-thiadiazolidine Z-rnethylaminothiobenzothiazole Z-dimethylaminothio benzothiazole Z-butylaminothiobenzothiazole 2-cyclohexylaminothio benzothiazole 2-decylaminothiopyridine 2-octadecylaminothio-4-phenyl-1,3,4-thiadiazole 2-(4-thiazolyl)benzimidazole 2-(2-methyl-4-thiazolyl) benzimidazole 2-(2-thiazolyl)benzimidazole 2-(2-thiazolinyl) benzimidazole 2-[ (4-thiazolyl) methyl]benzirnidazole 2-(2-thiadiaZol-1,3,4-yl) benzimidazole3-phenyl-l,3,4-thiadiazolidine-2,5-dithione3-ethy1-1,3,4-thiadiazolidine-2,5-dithione (4b) Monocyclic heterocycliccompounds chosen from and the remainder of the ring members being chosenfrom the groups in which R R and R have the definition given in (4a)above. These heterocyclic compounds can be chosen from amongstdithianes, trithianes and thiomorpholines.

Such compounds are for example the following:

1,4-dithiane 1,3,5-trithiane 2,4,6-trirnethyl-1,3,5-trithianethiomorpholine 3-oxo thiomorpholine 3-thioxo thiomorpholine 3-mercaptothiomorpholine 8. 3-bromo-N-methyl thiomorpholine2,4,6-trinitro-1,3,5-trithiane 3-amino thiomorpholine 3-decylaminothiothiomorpholine Z-acetamido-1,3,4-trithiane2-octadecylaminothio-1,3,4-trithiane 3-(4-n1ethoxy phenylazo)thiomorpholine 3-(2,4-dichloro phenylazo) thiomorpholine 3-(2-methylphenylazo) thiomorpholine (5) Thioic compounds defined by formula IV: u"fi' Q in which R Y, X and Q are chosen from those defined under (a), (b)and (c):

(a) The compounds in which R is a group chosen from hydrogen, alkyl or1-6 carbon atoms and an alkyl residue as just mentioned bearing asubstituent chosen from carboxy, alkoxy carbonyl having 2 to 5 carbonatoms, cyclo alkyl or alkyl cyclo alkyl containing 6 to 10 carbon atoms,phenyl, benzyl, or alkenyl containing 2 to 5 carbon atoms and X and Yrepresent an atom chosen from oxygen and sulphur, at least one of themper molecule being a sulphur atom; Q is chosen from among ot-a group Rselected from an alkyl containing 1 to 6 carbon atoms an alkyl carryinga group cyano, cycloalkyl containing 6 to 10 carbon atoms, alkylcycloalkyl containing 6 to 10 carbon atoms, pyridyl, phenyl, and phenylbearing one to three substituents chosen from fluorine, bromine, alkylof 1 to 4 carbon atoms, nitro, and hydroxy ,B-agroup B C 'Y-Ro in whichX, Y and R have the definition given above and in which B is chosen fromsulphur, a disulphid group and a hydrocarbon divalent group chosen fromalkylenes containing 1 to 8 carbon atoms and 1,2- 1,3- and 1,4-phenylenes. 'ya group-Z-R,, chosen among groups in which Z is oxygen orsulphur and R is a group chosen from those defined for R (b) Thecompounds in which R and Q form together an alkylene group containing 3to 10 carbon atoms in branched or straight chains;

(c) And compounds in which Q represents the group -ZR and in which R andR together form a divalent group chosen from aliphatic hydrocarbonchains containing 2 to 6 carbon atoms, 1,2-, 1,3-, and 1,4- phenylenes,cyclic systems containing 5 to 10 ring members and one or two rings,under which one of the two ring members are chosen from the grouphydrocarbons, the group=N and the group Such compounds are for examplethe following:

thioacetic acid thiopropionic acid thiobutyric acid dithiobutyric aciddithioacetic acid hexanethioic acid hexanedithioic acid hexane 1,6-bisthioic acid cyclohexane carbodithioic acid thiobenzoic aciddithiosalicylic acid 2,6-dichloro thiobenzoic acid 2-chlor-6-methylthiobenzoic acid 2-chloro-6-nitro thiobenzoic acid thionicotinic aciddithioterephthalic acid ethyl thioacetate methylthiobenzoatebenzylthioacetate diethyldithiolcarbonate diphenyldithiolcarbonateethanediyle-1,2-bis(dithiocarbonate) dibenzyltrithiocarbonatedimethyltrithiocarbonate thiophenylacetic acid dibutyltrithiocarbonate1,2-ethylene trithiocarbonate bis(carboxymethyl) trithiocarbonatebis(3-carboxypropyl) trithiocarbonate bis(methoxycarbonylmethyl)trithiocarbonate bis(butoxycarbonylmethyl) trithiocarbonatedihexyltrithiocarbonate dioctyltrithiocarbonateacetonitrile-O-isopropylthiocarbonate 1,2-phenylene trithiocarbonate2,3-quinoxalinediyletrithiocarbonate butyl ethyl xanthate methyl ethylXanthate phenyl ethyl Xanthate cyclohexylethyl Xanthatemethylethylxanthate benzylethylxanthate allylethylxanthatemethylbutylxanthate methylcyclohexyl Xanthate ethylbenzylxanthatebutylallylxanthate methylphenylxanthate phenylphenylxanthateethoxythiocarbonyl sulfide methoxythiocarbonyl disulfideethoxythiocarbonyl disulfide gamma thiobutyrolactone gammathioundecalactone 1,3-phenylene trithiocarbonate isopropyl thiocarbonyldisulfide methyl(4-butylcyc1ohexyl) Xanthate dicyclohexyltrithiocarbonate divinyltrithio carbonate (6) Thiamides defined by formula V:

in which R R and E are chosen as defined under (a) (a) R and R are eachseparately chosen from hydrogen, alkyl of 1 to 4 carbon atoms, phenyland taken together from an alkylene, straight or branched chain groupcontaining 4 to 10 carbon atoms, E represents a group chosen from agroup R as defined under R in a group --DC-N S Rlld in which Drepresents a symbol chosen from a direct bond or a divalent hydrocarbongroup chosen from alkylenes containing 1 to 8 carbon atoms andphenylenes and in which R and R have the same meaning as above.

(b) R and E represent a group such as defined under (b) in 5.

Such compositions are, for example, the following:

thioacetamide N,N-dimethyl thioacetamide N,N-dibutyl thioacetamidethiobenzamide 2,6 dichloro thiobenzarnide2,6-dihydroxy-N-ethylthiobenzamide 2,6-dichloro-N-ethyl thiobenzamide2-chloro-6-methyl thiobenzamide m 2,3,6-trichloro thiobenzamide2-chloro-6-nitro thiobenzamide 2-ch1oro-4-terbutyl thiobenzamide2-chloro-6-fluoro thiobenzamide 2-chloro-6-bromo thiobenzamidethioformamide thionicotinamide thioisonicotinamideN-thioacety1piperidine thioheptanoylarnide N-thioacetylpyrrolidinedithio malonamide 4-N-thioacetylpipecoline N,N-dimethylthiohexanoylamidedithioxamide dithiosuccinamide dithioadipamide dithiosebacamideN,N,N,N-tetramethyl dithioadipamide N,N-diethyl dithioadipamide N-phenylthioacetamide N-methyl N-phenyl thioacetamide dithiosuccinoyl bis-1,1(piperidine) gamma thiobutyrolactam epsilon thiocaparolactam gammathioundecalactam (7) Dithiocarbamic esters defined. by formula VI: (VI)/G T-SEIJN n in which R is chosen from hydrogen, alkyl of 1 to 4 carbonatoms and phenyl and in which T represents a group chosen from (a) Agroup R chosen from an alkyl containing 1 to 12. carbon atoms, alkenylcontaining 2 to 12 carbon atoms, benzyl, cycloalkyl or cycloalkenylcontaining 5 to 6 carbon atoms, cycloalkyl and cycloalkenyl such asdefined above bearing 1 to 3 alkyl substituents each containing 1 to 4carbon atoms, phenyl and a phenyl group carrying 1 to 3 substituentschosen from alkyl and alkenyl groups containing 1 to 5 carbon atoms,chlorine and nitro;

(b) A group R' -D's-fiN\ S }R IId in which D is alkylene straight orbranched chain containing 2 to 6 carbon atoms and R and R are chosensuch as defined in 6, and in which G is chosen from a group R' which hasone of the meanings given for R" defined above and a group -D'-liI-(H3-SRa,

11Hd S in which D, R and R" have the definition given above.

Such compounds are, for example, the following:

ethyl-N-methyl dithiocarbamate ethy1-N,N-dimethyl dithiocarbamatemethy1-N,N-dibutyl dithiocarbamate methyl-N,N-diethyl dithiocarbamateethyl N-methyl N-phenyl dithiocarbamate methyl N-ethyl N-phenyldithiocarbamate methyl N,N-pentamethylene dithiocarbamate ethylN,N-tetramethy1ene dithiocarbamate allyl N,N-dimethy1dithiocarbamatedodecyl N,N-dimethyl dithiocarbamate cyclohexylN,Ndimethyl dithiocarbamate cyclopenten-Z-yl-N-methyl dithiocarbamatementhyl N,N-dirnethyl dithiocarbamate phenyl N,N-dimethyldithiocarbamate 2,4-dinitrophenyl N,N-dipropyl dithiocarbamate2,4-dinitropheny1 N-ethyl N-methyl dithiocarbamate benzyl N,N-dirnethyldithiocarbamate 1 1 4-chlorophenyl, N,N-dimethy1 dithiocarbamate4-tertbutylphenyl N,N-dimethyl dithiocarbamate 4-pentyl phenylN,N-dimethyl dithiocarbamate 4(penten-2-yl)-phenyl N,N-dimethyldithiocarbamate N,N'-ethylene bis (methyl dithiocarbamate) N,N'-ethylenebis (butyl dithiocarbamate) N,N'-ethylene bis (2,4-dinitro phenyldithiocarbamate) N,N'-(2,3-butanediyl) bis (ethyl dithiocarbamate)N,N'-(3,4-hexanediyl) bis (ethyl dithiocarbamate) N,N'-ethylene bis(dodecyl dithiocarbamate) 1,2-ethane diyl bis(N,N-dimethyldithiocarbamate) 1,2-butane diyl bis(N,N-dimethyl dithiocarbamate)1,4-butane diyl bis(N,N-diethyl dithiocarbamate) (8) T hiocarbamicesters defined by formula VII v11 /R R -S(fiN\ in which R is chosen fromalkyl of 1 to 18 carbon atoms cyclo alkyl or alkyl cycloalkyl of 6 tocarbon atoms, phenyl and phenyl carrying 1 to 3 substituents chosen fromchlorine, nitro, and alkyl containing 1 to 4 carbon atoms,2-benzimidazolyl, 2-benzoxazolyl and 2- benzothiazolyl and R and M arechosen as defined under (a) and (b):

(a) R is chosen from groups defined for R," in 7 and M is a group chosenfrom the group R defined above, the group in which D" is chosen from a1,2-, 1,3-, or 1,4-phenylene group and a 1,2-, 1,3- and 1,4-phenylenegroup substituted by methyl and R has the signification .given above.

(b) R and M represent together an alkylene group containing 6 to 9carbon atoms.

Such compositions are for example the following:

N-methylcarbamoylthiomethane N,N-dimethylcarbamoylthiobutaneN-butylcarbamoylthiododecane N-phenylcarbamoylthiooctadecane1-N,N-diethylcarbamoylthio 2,5-dirnethyl cyclohexane1-N,N-diethylcarbamoylthio 2,5-diethyl cyclohexaneN-ethylcarbamoylthiobenzene 1-N-propylcarbamoylthio-4 nitro benzenel-piperidinocarbamoylthio 2,4,5-trichloro benzene l-(l-perhydroazecinyl)carbonylthio 2,5-dimethyl benzene 1-( l-perhydroazepinyl) carbonylthio4-tertiobutyl benzene 2-N-phenylcarbamoylthio benzirnidazoleZ-N-butylcarbamoylthio benzoxazole 2-N-propylcarbamoylthio benzothiazole1,2-bis(methylthiocarboxarnido) benzene 1,4-bis(phenylthiocarboxamide)benzene 1,4-bis(benzothiazoly1-2 thiocarboxamido) benzene2,4-bis(butylthiocarboxamido) toluene 2,4-bis(cyclohexylthiocarboxamide) toluene 2-N-(3-chloro phenyl) carbamoylthio benzimidazolemethyl N,N-dibenzyl thiocarbamate (9) Thiuram compounds defined byformula VlII:

(VIII) Rd R N-o-(s)no-N t it in which n is a whole number between 1 and6, R and R are chosen as given under 6 or in such a fashion that both Ron the one hand and two R on the other hand form together a phenylenegroup, an alkylene group containing 2 to 3 carbon atoms. Such compoundsare for example as follows:

(10) Isothiocyanic esters defined by the formula IX:

R N:C-=S

in which R is chosen from alkyl of 1 to 8 carbon atoms, phenyl andphenyl carrying 1 to 3 substituents chosen from alkyl of 1 to 5 carbonatoms, fluorine, chlorine, bromine, alkoxy and alkyl thio groupscontaining 1-4 carbon atoms and nitro.

Such compositions are, for example, the following:

methyl isothiocyanate ethyl isothiocyanate isopropyl isothiocyanatebutyl isothiocyanate octyl isothiocyanate phenyl isothiocyanate4-chlorophenyl isothiocyanate 2,4-dichlorophenyl isothiocyanate2-fluorophenyl isothiocyanate 4-bromophenyl isothiocyanate 4-nitrophenylisothiocyanate 3-cresyl isothiocyanate 4-tertbutylphenyl isothiocyanate2-methy1-4-tertbutylphenyl isothiocyanate anisyl isothiocyanate4-methylthiophenyl isothiocyanate 4-isobutoxyphenyl isothiocyanate4-pentylphenyl isothiocyanate (11) Thio areas defined by the formula X:

in which R is hydrogen, allyl, phenyl, or alkyl of 1-4 carbon atoms andW is chosen in one of the ways defined under (a) and (b).

1 Compound 2 Compound 3 Compound f Compound commonly calledethylenethluram sulphide. commonly called ethylene thiuram disulphide.commonly called ethylene thiuram trlsulphlde. h d commonly calledethylene thluram tetrasul-j 5 Compound phide.

Compound sulphide.

7 Compound phide.

commonly called propylene thluram tetrasulcommonly called paraphenylenethluram tetracommonly called piperazlne thiuram tetrasu1- in which D" isas defined in 8, R," is selected from an alkoxy carbonyl residuecontaining 2 to 5 carbon atoms and R; and R represent hydrogen.

Such compounds are, for example, the following:

Thiourea N,N-dipropylthiourea N-methylthiourea N-isopropylthioureaN,N-dimethylthiourea N-butylthiourea N,N-dimetl1ylthioureaN,N,N'-trimethylthiourea N-isobutylthiourea N-secbutylthioureatetramethylthiourea N-tertiobutylthiourea N-ethylthioureaN-allylthiourea N,N-diethylthiourea N,N-diallylthioureaN,N'-diethylthiourea N-phenylthiourea N-propylthiourea in which R R Rand R are chosen from the groups selected under (a) and (b) (a) R, ishydrogen, alkyl of 1-6 carbon atoms, methyl bearing one chlorine atom,phenyl, phenyl bearing one chlorine atom, alkoxy of 1-4 carbon atoms,phenoxy, phenoxy carrying one or two substituents chosen from chlorineand methyl, R R and R are the same or different and are hydrogen ormethyl.

(b) R; is chosen from 8-carboxyoctyl and 8-alkoxycarbonyloctyl in whichthe alkoxy group contains 1-8 carbon atoms, R and R are each hydrogenand R is octyl or 2,3-epithioocty1.

1 Such compounds are, for example, the following:

thiirane Z-methyl thiirane '2-ethyl thiirane 2,2-dimethyl thiirane2,3-dimethyl thiirane 2,2,3-trimethyl thiirane 2-butyl thiirane 2-hexylthiirane Z-methoxymethyl thiirane Z-ethoxymethyl thiirane2-isopropoxymethyl thiirane 2-butoxymethyl thiirane Z-phenoxymethylthiirane 2-phenyl thiirane 2-(4-chloro phenyl) thiirane2-(4-chlorophenoxymethyl) thiirane 2-(2,4-dichlorophenoxymethyl)thiirane 2-(4-methylphenoxymethyl) thiirane 2-chloromethyl thiirane9,10-epithio stearic acid 9,10,12,13-bis-epithio-stearic acid methyl9,10-epithio stearate butyl 9,10-epithio stearate octyl 9,10-epithiostearate ethyl 9,10,12,13-bis-epithio stearate (13) Sulfenamides definedby formula X11:

(X11) Rh Rh-S-N in which R is chosen irom methyl, methyl bearing 1-3substituents selected from chlorine and fluorine, ethyl, and ethylbearing l-5 substituents chosen from chlorine and fluorine.

R and R are chosen in one of the ways defined under (A), (B) and (C):

(A) R and R are hydrogen, alkyl of 1-4 carbon atoms, phenyl orcyclohexyl.

(B) R and R are chosen from the groups (A) and (B) as defined, the groupchosen in the group (B) being chosen from methylsulfonyl,ethy'lsulfonyl, phenylsulfonyl, chlorophenyl, andSO NXX", in which X andX" are selected from methyl, ethyl and phenyl.

(C) R and R form together a cyclic system selected from (a) a cyclicsystem comprising l-10 ring members and 1 or 2 rings in Which thenitrogen atom is one of the ring members, a second ring member beingchosen from a hydrocarbon member, sulphur, oxygen and nitrogen and theother ring members being hydrocarbon ring members.

(b) a cyclic system as defined under (a) and carrying one or twocarbonyl oxygen atoms.

Such compounds are, for example, the following:

N-(ethylthio) butylamine N-(methylthio) butylamineN-(trichloromethylthio) dibutylamine N-(trichloromethylthio)dicyclohexylamine N-(trichloromethylthio) succinimideN-(trichloromethylthio) phthalirnide N-(trichloromethylthio)'benzoxazolone N-(trichloromethylthio) benzothiazoloneN-(trichloromethylthio) benzimidazolone N-(dichlorofiuoromethylthio)tetrahydrophthalimide N- (dichlorofiuoromethylthio phthalimide N- 1,1,2,2,-tetrachloroethylthio) tetrahydrophthalimide N-(trichloromethylthio N- (methylsulfonyl) 4-chloroanilineN-(trichloromethylthio) N-(ethylsulfonyl) anilineN-(trichloromethylthio) N-(phenyllsulfonyl) anilineN-(trichloromethylthio) N-(diethy'lsulfamoyl) propylamineN-(dichlorofluoromethylthio) N-(dimethylsulfamoyl) anilineN-(trichloromethylthio) N-(methylphenyl sulfamoyl) methylamineN-(methylthio) aniline N-(chloromethylthio) dipropylamineN-(trifluoromethylthio) cyclohexylamineN-(2-chloro-1,1,2,2-tetrafiuoroethylthio) phthalimideN-trichloromethylthiotetrahydrophthalimide N-(ethylthio) diphenylamineN-(trichloromethylthio) dimethylamine (14) Sulfenic esters defined byformula XIII: (XIII) R --S--OR in which R is as defined in 13 and R isselected from phenyl, phenyl carrying 1-3 substituents chosen fromchlorine, nitro, and alkyl and alkoxy containing 1-4 carbon atoms,naphthyl and quinolyl.

Such compounds are, for example, the following:

(l) Thio ketones defined by formula XIV: (XIV) RifiRi' in which R, and Rare chosen from alkyl of 1-4 carbon atoms, alkyl of 1-4 carbon atomscarrying 1-9 fluorine atoms, cyclohexyl, phenyl, and phenyl carrying lor 2 substituents selected from alkyl and alkoxy groups containing 1-4carbon atoms.

Such compounds are, for example, the following:

thioacetone 2-thioxobutane 3-thioxopentane 4-thioxoheptane2,6-dimethyl-4-thioxoheptane thioacetylcyclohexanedicyclohexylthioketone 1,3-difluorothioacetone perfluorothioacetone4-perfluoroheptanethione Z-perfiuorohexanethione1,1,1,3,3,4,4-heptafiuorobutane-Z-thione thioacetophenonethiobutyrophenone cyclohexylcarbothioylbenzene2,4-dimethylthioacetophenone o-methoxy thiopropiophenone4-methoxy-2-methyl thio acetophenone 4,4'-dimethoxy thiobenzophenone2,2',4,4'-tetrarnethoxy thiobenzophenone 2,2'-dimethyl thiobenzophenone'2,2',4,4'-tetramethyl thiobenzophenone p-butoxyacetophenone 2,4-dibutylthioacetophenone (16) Derived salts:

of mercaptans defined in 2 and 4,

of thioic acids defined in 5,

of sulphanes defined in 1 of acids corresponding to the thio carbamicesters defined in 7 and 8 in which the cationic portion is selected frommetals such as sodium, potassium, calcium, zinc, cadmium, copper,nickel, cobalt, iron, manganese, silver, lead, barium, strontium andaluminium and an ammonium ion chosen from ions derived from ammonia andions derived from amines containing 1-3 groups chosen from alkyl groupsof 1-4 carbon atoms and phenyl groups such as, for example, methylamine,dimethylamine, trimethylamine, diethylamine, triethylamine, butylamine,dibutylamine, tributylamine, methylaniline and dimethylaniline and ionsderived from a nitrogen heterocycle such as pyridinegmorpholind' isbetter when they do not contain any acid by-products;

the sulphur compound now having lost its cation preserves itsstabilising properties and then acts for a second time.

The solvents for the phosphoric ester can advantageously be hydrocarbonsof the aliphatic, alicyclic or aromatic series which are solid or liquidat ambient temperature" under pressure or otherwise. Such solvents maybe'usetl separately or in admixture. Their solvent power for thephosphoric ester and/or the stabiliser may be optionally reinforced bythe addition of co-solvents which may be chosen from the groups ofaliphatic ketones, hydroxylated compounds, ethers, esters, amides,nitriles and halogenated hydrocarbons.

Other solvents usable in compositions according tothe present inventionare halogenated hydrocarbons, ethers, and esters formed by aliphatic,cyclo aliphaticor ara l-, coylic alcohols or phenols and aliphatic acidsor di acids such as phthalic acid, sebacic acid and adipic acid, oragain phosphoric esters which are not pesticides such as the phosphorictriesters of methyl, ethyl, butyl, oct-yl, decyl, dodecyl, phenyl,cresyl, diphenyl, tert.butylphenyl. The solvents usable in thecompositions according to the present invention can also be solidcompounds such as, for example, organic synthetic resins, such ashomopoly mers and copolymers formed starting from vinyl derivatives(acetate, propionate, butyrate, oxides, formal, acetal, butyral,chloride, etc.) and/ or vinylidene derivatives and/ or alkenes(ethylene, propylene, butylene) and/ or styrene and/or vinylpyrrolidones, and/or cellulose derivatives" (methyloxide, ethyloxide,benzyloxide,vacetate, propion-.

ate, butyrate, phthalate, nitrate) and/or isoprene, and/o'r' butadieneand/or acrylic or methacrylic esters and/or allyl esters (phthalate,isophthalate, maleate, cyanurate),

the action of a poly acid on a polyol, and polyurethanes resulting fromthe condensation of a polyisocyanate with a polyol of coumarone indeneresins. Solid compounds able to serve as solvents can also be naturalresins, such as colophane, shellac, tallol or a waxy resin.

Among inert mineral adjuvants which may be used in compositionsaccording to the present invention the following should be noted: brick,pumice, vermiculite,dried clay, calcium carbonate, pyrophyllite,dolomite, glass fibre, plaster, talc, natural silica, fossil orotherwise, artificial silica and metallic oxides. Amongst inert organicadjuvants which may be used in compositions according to the inventionthere may be noted, for example, wood" flour, cellulose fibre, starch,faecula, sugars and/or' 'diluents which are only slight solvents such asp'arafiin,-' which can have its properties modified by the addition oforganic synthetic resins and/or of'salts formed ubyi alkoylaminoalkoylamines and aliphatic acids and/or, aminated derivatives ofmontmorillonite such as bentones- Complementary stabilisers areadvantageouslychosen' from oxiranes, such as epoxidised oil such asapoxidised soya oil, al'koylepoxy stearates and epoxyhaloalkanes or fromazoic compounds or their metalliferous derivatives;

Compositions according to the present invention can also contain one ormore natural or synthetic aromatic,

materials, one or more complementary active materials such asacaricides, insectifungal agents, bird repellants,

antifungal agents, growth regulating agents, herbicides or bactericides.

So formulated, the compositions according to the pres ent invention maybe solid or liquid. They may be disposed on a solid porous or fibroussupport. This support can be constituted for example by a paper, a feltof wool, cotton and/or synthetic fibres or a compressed cellulose suchas wood fibres, cereal fibres, alfalf-fibres and cotton fibres, feltcard, a card of old papers or a card of glass fibre.

According to one valuable mode of application of the invention the solidporous or fibrous support for the composition may be lined with apermeable membrane constituting a diffusion surface and consisting, forexample, of a layer of polyethylene or polypropylene or of a mixturethereof or a copolymer of ethylene and propylene or of a copolymercomprising vinylindene chloride; preferably such a membrane should beconstituted by a layer of polyethylene of thickness 1018 microns;examples of such devices are described in French Pat. No. 1,590,647 ofJuly 12, 1968.

Such compositions are advantageously used as insecticidal products. Thepresence of a body of sulphur containing material as stabiliser conferson the phosphoric ester a heightened resistance to the destructiveeffect of water contained in the composition and in the ambienthumidity, as is shown by the following experiments which are merelygiven as examples. So called experiments carried out by the applicantsare now set forth in order to enable a better understanding of thatwhich has gone before.

EXPERIMENT 1 Sheet 5 x cm. cut from a cellulose card made by the FrenchCompany Fioroni S.A. under reference 200 were used; at the moment of usethe card weighed 875 g./rn.

The sheets of card were bonded in twos, back to back by means ofstaples; these doubled cards were divided into two series denoted l-Aand l-B.

The doubled cards 1-A were each impregnated with 12.5 g. DDVP (commonname for 0,2,2-dichlorovinyl 0,0-dimethyl phosphate) and the doubledcard 1B were each impregnated with 12.5 g. of a 1% by weight solution ofhydrogen sulphide in DDVP. The solution had been obtained by passinghydrogen sulphide in gaseous form into the DDVP.

The so-impregnated doubled cards were suspended in a room thetemperature of which was kept at 22 :2 C. and the relative humidity ofwhich was about 42.

At the end of 8 days the quantity of DDVP destroyed by hydrolysis wasmeasured potentiometrically (it has been established by others that thehydrolysis of DDVP in the conditions of exposure above leads to an acidphosphoric ester and that the potentiometric value of the single acidityor of the first acidity of this ester permit the quantity of DDVPhydrolysed to be established).

The acidity present in the DDVP (1.0% equivalent DDVP) was taken intoaccount and this was deducted from the results obtained. Percentagequantities of DDVP decomposed by hydrolysis which were determined areexpressed in the table below: the values preceded by the 1- signrepresent the dispersion of the results in each serles A l-B 24.1 2.0

EXPERIMENT 2 Doubled cards were used as described in Experiment 1 but ofweight 885 g./m. These cards were divided into four series called 2A to2-D. Each card 2-A was impregnated with 12.5 g. DDVP. The other doubledcards were impregnated each with 12.5 g. of DDVP after having beenimpregnated with 0.25 g. of one of the fol-. lowing salts and dried:

2-B: disodium sulphide 2-C: disodium polysulphide 8 2-Dc disodiumtetrasulphide The thus impregnated cards were suspended in a room, thetemperature of which was kept at 21 i2 C. and the relative humidity ofwhich was about 65.

At the end of 15 days the percentage quantities of DDVP destroyed weremeasured as noted in Experiment 1 and tabulated as follows:

The results of Experiments 1 and 2 show to what degree the DDVP issensitive to humidity when it is not protected. They also show thathydrolysis can be reduced in substantial degree when a sulphane or asalt thereof is added to phosphoric ester.

EXPERIMENT 3 Double cards were used as described in Experiment 1 but ofweight 870 g./m. These double cards were divided into two series called3-A and 3-B. Cards 3-A were each impregnated with 12.5 g. DDVP. Cards3-B were each impregnated with 12.5 g. of a 1% by weight solution ofZ-mercapto pyridine in DDVP. The thus impregnated cards were suspendedin a room of which the temperature was kept at 22 :2 C. and the relativehumidity of which was about 40.

At the end of 15 days the percentage quantities of DDVP destroyed weremeasured as noted in Experiment 1 and tabulated at follows:

EXPERIMENT 4 Cards of size 10 x 10 cm. cut from a cellulose card made bythe French company Fioroni S.A. under reference 200 were used; at themoment of use the card weighed 875 g./m.

The card squares were divided into three series of three numbered unitsof 4-A and 4-B; squares 4-A were each impregnated with 17 g. DDVP andthe other squares were 1 EXPERIMENT 5 Card squares were used asdescribed in Experiment 4 but of weight 870 g. m. These cards weredivided into three series S-A to 5-C. Cards 5-A were each impregnatedwith 12.5 g. DDVP; the other cards were each impregnated with 12.5 g. ofa solution of 1,10-decanedithiol' in DDVP at the followingconcentrations:

Percent 1 Mixture of disodium trisulphide, tetrasulphide, peIttQL-Esulphide and hexasulphide.

19 The thus impregnated cards were suspended in a room, the temperatureof which was kept at 22 :12 C. and the relative humidity of which wasabout 40.

At the end of days the percentage quantities of DDVP destroyed weremeasured as noted in Experiment 1 and tabulated as follows:

5-A 5-B 5-C 22. 2 1. 6 1. 3 :bl. 1 :l:0. 03 :lzO. 1

EXPERIMENT 6 Squares of card were used as described in Experiment 4 butof weight 60 g./m. These cards were divided into two series called 6Aand 6B; cards with 6A were each impregnated with 14.2 g. DDVP; cardswith 6-B were each impregnated with 14.2 g. of a 1% solution ofZ-mercaptobenzimidazole in DDVP.

The so-impregnated cards were suspended in a roomthe temperature ofwhich was kept as :2 C. and the relative humidity of which was about 35.

At the end of 12 days, the percentage quantity of DDVP destroyed weremeasured as noted in Experiment 1 and tabulated as follows:

EXPERIMENT 7 7-A 7-B 28.8 4.0 -2.7 i0.5

EXPERIMENT 8 Doubled cards were used as described in Experiment 1 but ofweight 900 g./m. These cards were divided into two series 8-A and 8-B.The doubled cards 8-A were impregnated with 12.5 g. DDVP, While theother doubled cards were each impregnated with 12.5 g. of a 3% solutionof Z-mercapto-l-methylimidazole in DDVP.

The so-impregrated cards were suspended in a room, the temperature ofwhich was kept at 22 :2" C. and the relative humidity of which was about75.

At the end of 14 days, the percentage quantities of DDVP destroyed weremeasured as noted in Experiment 1 and tabulated as follows:

EXPERIMENT 9 9- B: 2% Z-mercaptoethyI-Z-mercapto acetate 9--C: "3%bis-(Z-mercapto acetate) ethane-1,2,-diyl 9-D: 3% l-mercapto octadecane9-E: 3% strontium thioglycolate 20 The so impregnated cards weresuspended in a room, the temperature of which was kept at 20 112C. andthe relative humidity of which was about 60.

At the end of 10 days, the percentage quantities of DDVP destroyed weremeasured as given in Experiment 1 and tabulated as follows:

The results of Experiments 3-9 show that the hydrolysis of a phosphoricester such as DDVP can be reduced to a substantial extent when a sulphurcompound chosen from organic compounds having at least one mercaptangroup is added to the phosphoric ester.

EXPERIMENT 10 Doubled cards were used as described in Experiment 1 butof weight 900 g./m. These double cards were divided into seven seriescalled 10-A to IO-F; cards 10-A were each impregnated with 12.5 g. DDVP;the other cards were impregnated each with 12.5 g. of a 2% solution inDDVP of one of the following compounds:

IO-B :Z-methylthio benzimidazole 10-Czdidecy1 sulphide 10D:dioctyldisulphide lO-Erdi-Z-pyridyl disulphide 10-F:l,6-dicarboxy-3,4-dithiahexane (compound commonly called3,3-dithiodipropionic acid The thus impregnated cards were suspended ina room, the temperature of which was kept at 22i2 C. and the relativehumidity of which was about 70.

At the end of 10 days the perecentage quantitives of DDVP destroyed weremeasured as given in Experiment 1 and tabulated as follows:

l0A IO-B 10-C 10-D 10-13 10-]? 21. 2% 1. 9 0 0 0 4. 0 :i:0. 8% i0. 2:l:0. 4

EXPERIMENT 11 1l-A 11-B 22.2 0

EXPERIMENT l2 Doubled cards were used as described in Experiment 1 butof weight 900 g./m. These cards were divided into three series 12-A tol2-C. Cards 12-A were impregnated each with 12.5 g. DDVP. The otherdoubled cards were each impregnated with 12.5 g. of a 3% solution inDDVP of one of the following compounds:

12-B di-4-morpholinyl disulphide 12C:2-morpho1inothio benzothiazole Thethus impregnated cards were suspended in a room,

the temperature of which was kept at 22i2 C. and the relative humidityof which was about 75. 1

At the end of 14 days, the percentage quantities of DDVP destroyed weremeasured as given in Experiment 1 and tabulated as follows:

12-A 12-B 12-C EXPERIMENT 13 Doubled cards were used as described inExperiment 1 but of weight 880 g./m. These cards were divided intofifteen series called 13-A to 13-0. Cards 13-A were each impregnatedwith 12.5 g. DDVP. The other doubled cards were each impregnated 12.5 g.of a 2% solution in DDVP of one of the following compounds:

The thus impregnated cards were suspended in a room,

EXPERIMENT 15 Squares of card were used as in Experiment 4 divided intotwo series l5-A and l5-B; squares 15-A were each impregnated with 17 g.of DDVP and squares 15-B were each impregnated with 17 g. of a 1%solution in DDVP of 2 [(4-thiazolyl)methyl] benzimidazole.

These squares were suspended in a room, the temperature of which waskept at 231-2 C. and the relative humidity of which was about 57.

At the end of 7 days, the quantity of DDVP destroyed by hydrolysis wasmeasured as in Experiment 1; the percentage quantities of DDVP thusdecomposed are indicated in the following table:

EXPERIMENT 16 Card squares were used as in Experiment 4 which weredivided into two series numbered 16-A and 16-B; squares 16-A were eachimpregnated with 17 g. of DDVP and the other squares were eachimpregnated with 17 g. of a 1% solution in DDVP of2(4-thiazo1yl)benzimidazole.

The thus impregnated squares were suspended in a room, the temperatureof which was kept at 2012" C. and the relative humidity of which wasabout 45.

At the end of 14 days, the quantity of DDVP destroyed by hydrolysis wasmeasured as in Experiment 1. The percentage quantities of DDVPdecomposed are indicated in the following table:

the temperature of which was kept at 20i2 C. and the relative humidityof which was about 60. 275 H w u u u At the end of 15 days, thepercentage quantities of +13 +04 DDVP destroyed were measured as givenin Experiment 1 and tabulated as follows:

13-11 13-13 13-0 13-D 13-E 13-1 13-G 13-11 13-1 13-1 13-1: 13-L 13-M13-N 13-0 10. a 0. 5 1. a 1. 9 0 0.1 0.3 0.6 0.6 6. 6 0. 2 4. 0 1. 3 0.04 0 10.3 $003 =|=0.02 $0.3 i0 5:0. 01 5:0. 02 5:0.01 5:0.4 5:0. 01 5:0$0.2 i0

The results of Experiments 10 to 13 show that the hy- EXPERIMENT 17drolysis of the phosphoric ester such as DDVP can be 4.5

easily controlled when a sulphur compound chosen from sulphides is addedto this ester.

EXPERIMENT 14 Card squares were used as described in Experiment 4. Thesecards were divided into four series 14-A to 14-D. Cards 14A were eachimpregnated with 12.5 g. of DDVP; the other cards were each impregnatedwith 12.5 g. of a 1 or 2% solution in DDVP of one of the followingcompounds:

I l-A I l-B 14-1) 22. 2 0. 9 2. 2 1. 4 dzl. 1 :l:(). 06 i0. 6 3:0. 02

B Mixture titrating 31.5% of sulphur containing about 20% oftetrasulphide, 73% 1of pentasulphide and 10% of hexasulhid of ditertiodoecy p Eompound known under the name of bismu thiol II.

Doubled cards were used as described in Experiment 1 but of weight 900g./m. These cards were divided into two series 17-A and 17B. The doubledcards 17A were each impregnated with 12.5 g. of DDVP. The other doubledcards were each impregnated with 12.5 g. of a 2% solution in DDVP of1,3,5-trithiane.

The thus impregnated cards were suspended in a room, the temperature ofwhich was kept at 22:2" C. and the relative humidity of which was about70.

At the end of 10 days, percentage quantities of DDVP destroyed weremeasured as given in Experiment 1 and tabulated as follows:

EXPERIMENT 18 Card squares were used as described in Experiment 4 but ofweight 880 g./m. These cards were divided into three series 18-A to18-C. The cards 18-A were each impregnated with 17 g. DDVP. The othercards were each impregnated with 17 g. of a. 1% solution in DDVP of oneof the following compounds:

18-13: Z-mercapto benzothiazole 18-C: phenothiazine The thus impregnatedcards were suspended in a room the temperature of which was kept at 20:2C. and the relative humidity of which was between 55 and 60.

At the end of 15 days, the percentage quantities of DDVP destroyed weremeasured as given in Experiment 1 and tabulated as follows:

18-A 18-B 18-C 30.4 4. 8 13. 6 i2. 2 :lzO. 4 it]. 4

EXPERIMENT 19 Doubled cards were used as described in Experiment 1 butof weight 885 g./m. These cards were divided into five series called19-A to l9-E. Cards 19-A were each impregnated with 12.5 g. DDVP. Theother doubled cards were each impregnated with 12.5 g. of a solution inDDVP of one of the following compounds at the concentration given:

19-B: 2% of 2-methoxyphenothiazine 19-C: 1% of 3-oxothiomorpholine 19-D:1% of 4-oxo-2-thioxo thiazolidine 19-E: 1% of 3-methyl-4-oxo-2-thioxothiazolidine The thus impregnated cards were suspended in a room, thetemperature of which was kept at 21:2 C. and the relative humidity ofwhich was about 65.

At the end of 15 days, the percentage quantities of DDVP destroyed weremeasured as given in Experiment 1 and tabulated as follows:

34. 2 0. 7 0. ()6 I. 7 0. 3 i0. 8 :i:(). 04 :1:0 i0. 06 i% EXPERIMENT 20Doubled cards were used as described in Experiment 1 but of weight 900g./m. These cards were divided into three series denoted 20-A to 20-C.Cards 20-A were each impregnated with 12.5 g. DDVP. The other doubledcards were each impregnated with 12.5 g. of a solution at 2% in DDVP ofone of the following compounds:

20-B: 2-cyclohexylaminothio benzithiazole 20-C:3-methyl-2-oxobenzothiazoline The thus impregnated cards were suspendedin a room, the temperature of which was kept at 2212 C. and of which therelative humidity was between 70 and 75.

At the end of days, the percentage quantities of DDVP destroyed weremeasured as given in Experiment 1 and tabulated as follows:

-A 20B 20-C EXPERIMENT 21 21-A 2l-B 35.3 3.9

The results of Experiments 14 to 21 show that the hydrolysis of thephosphoric ester such as DDVP can be reduced in substantial proportionwhen a sulphur com- 214 pound chosen from heterocyclic compounds isadded to this ester.

EXPERIMENT 22 Card squares were used as described in Experiment 4; thesecards were divided into two series 22A and 22B; cards 22A were eachimpregnated with 15 g. DDVP; cards 22-B were each impregnated with 15 g.of a 1% solution of thiobenzoic acid in DDVP.

The thus impregnated cards were suspended in a room, the temperature ofwhich was kept at 23:2 C. and of which the relative humidity was about60.

At the end of 8 days, the percentage quantities of DDVP destroyed weremeasured as given in Experiment 1 and tabulated as follows:

22A 22-B 35.3 12:0 $1.6 i0.2

EXPERIMENT 23 Doubled cards were used as described in Experiment 1 butof weight 895 g./m. These cards were divided into three series 23-A to23-C. Cards 23-A were each impregnated with 12.5 g. DDVP; the otherdoubled cards were each impregnated with 12.5 g. of a -1.5 solution inDDVP of one of the following compounds:

23-B: methylbutylxanthate 23-C: bis (ethoxycarbonyl) disulphide The thusimpregnated cards were suspended in a room, the temperature of which waskept at 22i2 C. and the relative humidity of which was about 70.

At the end of 15 days, the percentage quantities of DDVP destroyed weremeasured as given in Experiment 1 and tabulated as follows:

36. 8 4. 3 0 :l:2. 4 :lzO. 8

EXPERIMENT 24 Card squares were used as described in Experiment 4. Thesecards were divided into three series 24-A to 24C. Cards 24-A were eachimpregnated with 12.5 g. of DDVP; the other cards were each impregnatedwith 12.5 g. of a solution at one or two percent in DDVP of one of thefollowing compounds:

24-B: 1% of potassium butyl trithiocarbonate 24-C: 2% of potassium butyltrithiocarbonate The thus impregnated cards were suspended in a room,the temperature of which was kept at 22:2 C. and of which the relativehumidity was about 40.

At the end of 15 days, the percentage quantities of DDVP destroyed weremeasured as given in Experi ment 1 and tabulated as follows:

22. 2 2. 1. 7 :|:1. 1 it). 4 :i:(). 03

EXPERIMENT 25 Doubled cards were used as described in Experiment 1 butof weight 900 g./m. These cards were divided into two series 25-A and25-B. Cards 25-A were each impregnated with 12.5 g. of DDVP. The otherdoubled cards were each impregnated with 12.5 g. of a 2% solution inDDVP of zinc isopropyl xanthate.

The thus impregnated cards were suspended in a room, the temperature ofwhich was kept at 22i2 C., and the relative humidity of which was about75.

25 At the end of 15 days, the percentage quantities of DDVP destroyedwere measured as given in Experiment 1 and tabulated as follows:

EXPERIMENT 26 Doubled cards were used as described in Experiment 1 butof weight 880 g./m. These cards were divided into seven series called26-A to 26-6. Cards 26-A were each impregnated with 12.5 g. of DDVP. Theother doubled cards were each impregnated with 12.5 g. of a 2 or 3%solution in DDVP of one of the following compounds:

2 6B: 2% of bis(carboxymethyl) trithiocarbonate 26-0: 3% ofdibenzyltrithiocarbonate 26D: 3% of ethylene trithiocarbonate 26-Et 3%of isopropylthiocarbonyldisulphide 26-F: 3% of potassium thioacetate26G: 3% of zincthiobenzoate The thus impregnated cards were suspended ina room, the temperature of which was kept at 20:2 C. and the relativehumidity of which was 60.

At the end of 10 days, the percentage quantities of DDVP destroyed weremeasured as given in Experiment 1 and tabulated as follows:

ZG-A 26-13 26-C 26-D 26-E 26-F 26-G The results of Experiments 22 and 26show that the hydrolysis of a phosphoric ester such as DDVP can bereduced in notable proportion when a sulphur compound chosen from thioiccompounds or salts thereof is added to this ester.

EXPERIMENT 27 Card squares were used as described in Experiment 4 but ofweight 870 g./m. These cards were divided into three series called 27A,27B and 27-C. Cards 27A were each impregnated with 17 g. DDVP; the othercards were each impregnated with 17 g. of a 1% solution in DDVP of oneof the following compounds:

27-B: thiobenzamide 27C: thionicotinamide The thus impregnated cardswere suspended in a room, the temperature of which was kept at 23 :2" C.and the relative humidity of which was about 60.

At the end of 8 days the percentage quantities of DDVP destroyed weremeasured as given in Experiment 1 and tabulated as follows:

EXPERIMENT 28 26 EXPERIMENT 29 Card squares were used as described inExperiment 4. These cards were divided into two series 29-A and 29-B.Cards 29-A were each impregnated with 12.5 g. of DDVP; cards 29-B wereeach impregnated with 12.5 g. of a 1% solution in DDVP of 2,6-dichlorothiobenzamide (a compound known under the common name of chlorthiamide).

The thus impregnated cards were suspended in a room, the temperature ofwhich was kept at 22:2 C. and the relative humidity of which was about40.

At the end of 15 days, the percentage quantities of DDVP destroyed weremeasured as given in Experiment 1 and tabulated as follows:

29-A 29-3 22.2 1.0 ill $0.1

EXPERIMENT 30 Doubled cards were used as described in Experiment 1 butof weight 900 g./m. These cards were divided into three series 30-A to30-0. Cards 30-A were each impregnated with 12.5 g. of DDVP. The otherdoubled cards were each impregnated with 12.5 g. of a 0.5 and 1%solution in DDVP of thioisonicotinamide.

30-B: 0.5% of thioisonicotinamide 30C: 1% of thioisonicotinamide Thethus impregnated cards were suspended in a room, the temperature ofwhich was kept at 22:2 C. and the relative humidity of which was about75.

At the end of 20 days, percentage quantities of DDVP destroyed weremeasured as given in Experiment 1 and tabulated as follows:

EXPERIMENT 31 31B: epsilon thiocaprolactam 31-C: dithiooxarnide The thusimpregnated cards were suspended in a room, the temperature of which waskept at 20:2 C. and the relative humidity of which was about 60.

At the end of 10 days, the percentage quantities of DDVP destroyed weremeasured as given in Experiment 1 and tabulated as follows:

The results of Experiments 27 to 31 show that the hydrolysis of aphosphoric ester such as DDVP can be reduced by substantial proportionwhen a sulphur compound chosen from thiamides is added to this ester.

EXPERIMENT 32 Card squares were used as described in Experiment 4. Thesecards were divided into seven series 32-A to 32-6. Cards 32-A were eachimpregnated with 12.5 g. of DDVP; the other cards were each impregnatedwith 12.5 g. of a solution in DDVP of one of the following compounds atthe concentration given:

32-Bz 1% of methyl N,N-diethyldithiocarbamate 32C: 1% of ethylN,N-diethyldithiocarbamate 32-Dz 1% of methyl N,N-dibutyldithiocarbamate5 32-E: 2% of methyl N,N-dibutyldithiocarbamate 32-F: 1% of methylN,N-pentamethylene dithiocarbamate 32-G: 2% of methyl N,N-pentamethylenedithiocarbamate The thus impregnated cards were suspended in a room, thetemperature of which was kept at 22:2 C. and the relative humidity ofwhich was about 65.

28 to 35-]; cards 35-A were each impregnated with 12.5 g. DDVP; theother cards were each impregnated with 12.5 g. of a solution in DDVP ofone of the following compounds at the concentration given:

35B: 1% of zinc N,N-diethyldithiocarbamata 35-C: 2% of zincN,N-diethyldithiocarbamate 35D: 0.5% of cadmiumN,N-diethyldithiocarbamate 35-E: 1% of cadmiumN,N-diethyldithiocarb'amate 35-F: 0.05% of ferricN,N-diethyldithiocarbamate 35-6: 0.3% of cupricN,N-diethyldithiocarbamate 35-H: 0.05% of silverN,N-diethyldithiocarbamate 35-1: 1% of zincN-ethyl-N-phenyldithiocarbamate 35J 2% of zincN-ethyl-N-phenyldithiocarbamate At the end of days, percentagequantities of DDVP 15 destl'oycd Were measured as given in Experiment 1and The thus impregnated cards were suspended in a room, tabulated asfollows! the temperature of which was kept at 22:2 C. and the relativehumidity of which was about 65. 32 A 32-13 32-0 32-1) 32-15 32']? At theend of 15 days, the percentage quantities of 043 Q7 (16 20 DDVPdestroyed were measured as given in Experiment $1.4 $005 $0. 02 $01$0.03 $0.00 $0.01 1 and tabulated as follows:

-A 35B 35-0 35-D 35-12 35-1 35-G 35-11 35-1 35-J EXPERIMENT 33 30EXPERIMENT 36 Double cards were used as those described in Experi-Doubled cards were used as described in Experiment ment 1 but of weight890 g./m. These doubled cards 1. These doubled cards were divided intothree series were divided into two series 33-A and 33-B; double cards36-A to 36C; cards 36-A were each impregnated with 33A were eachimpregnated with 12.5 g. of DDVP; the 12.5 g. DDVP; the other cards wereeach impregnated other doubled cards were each impregnated with 12.5 g.39 with 12.5 g. of a solution in DDVP of one of the follow.- of asolution in DDVP at 2% of zinc N,N-dibutyldithioing compounds at theconcentration given:

carbamate.

The thus impregnated cards were suspended in a room, 3643: 1% of ZlncNN'dmethy1d1th1carbflmajte f the temperature of which was kept at 22:2C. and the 40 36'C: of Zmc ethylene blsmlthlocarba relative humidity ofwhich was about 75. mate) At the end of 15 days, the percentagequantities of The thus impregnated cards were suspended in aroom, DDVPdestroyed were measured as given in Experiment the F P F of whlqh waskept at 22:2 and the 1 and tabulated as follows: relative humidity ofwhich was about 45.

-At the end of 8 days the percentage quantities of DDVP 33-13 4.5destroyed were measured as given in Experiment 1 and tabulated asfollows: :0.6 :0.07

EXPERIMENT 34 3643 31.2 1.3 1.2 Card squares were used as thosedescribed in Experi- :19 :0.15 :02

ment 4. These cards were divided into three series 34-A to 34-C; cards34-A were each impregnated with 12.5 g. of DDVP; the other cards wereeach impregnated with 12.5 g. of a solution in DDVP of one of thefollowing compounds at the concentration of 1%:

34-B: zinc N,N-dimethyl dithiocarbamate 11 34-C: zinc N,N-diethyldithiocarbamate EXPERIMENT 35 Squares of card were used as described inExperiment 4. These cards were divided into ten series denoted 35-ACompound known under the common name of zirame.

EXPERIMENT 37 Doubled cards were used as described in Experiment 1 butof weight 885 g./m. These cards were divided into ten series 37-A to37-J. Cards 37.-A were each impregnated with 12.5 g. DDVP; the otherdoubled cards were each impregnated with 12.5 g. of a 1% solution inDDVP of one of the following compounds:

37-B: 37-C: 37-D: 37-E: 37-F:

The thus impregnated cards were suspended in a room, the temperature ofwhich was kept at 21:2 C. and the relative humidity of which was about65.

At the end of 15 days, the percentage quantities of 12 Compound knownunder the common name of zlnebe.

DDVP destroyed were measured as given in Experiment 1 and tabulated asfollows:

37-.A 37-13 37-0 37D 37-E 37-F 37-G 37-11 37-I 37-1 34. 2 0. 3 0. 06 00. 5 0.5 0. 3 0 0. 6 :lzO. 8 i0. 01 i0 i0. 03 i0. 06 :kO i0. 0

EXPERIMENT 38 Doubled cards were used as described in Experiment 1 butof weight 890 g./m. These cards were divided into two series 38-A and38-B. Cards 38-A were each impregnated with 12.5 g. DDVP. The otherdoubled cards were each impregnated with 12.5 g. of a 3% solution inDDVP of 2,4 bis(butylthiocarboxamido) toluene. The thus impregnatedcards were suspended in a room, the temperature of which was kept at22:2 C. and of which the relative humidity was about 75.

At the end of days the percentage quantity of DDVP destroyed weremeasured as is given in Experiment 1 and tabulated as follows:

EXPERIMENT 39 Card squares were used as described in Experiment 4 but ofweight 860 g./m. These cards were divided into two series 39-A and 39-B.Cards 39-A were impregnated each with 17 g. DDVP. The other cards wereimpregnated each with 17 g. of a 1% solution in DDVP of 2[N(3-chlorophenyl)carbamoylthio] benzirnidazole.

The thus impregnated cards were suspended in a room, the temperature ofwhich was kept at 20i2 C. and the relative humidity of which was about45.

At the end of 14 days, the percentage quantities of DDVP destroyed weremeasured as in Experiment 1 and tabulated as follows:

39-A 39-B 27.5 9.3 :1 3 i- 1.0

The results of experiments 38 and 39 show that the hydrolysis of aphosphoric ester such as DDVP can be reduced to a very great degree whena sulphur compound chosen from thiocarbamic esters is added to thisphosphoric ester.

EXPERIMENT 40 Squares of card were used as described in Experiment 4.These cards were divided into three series 40-A to 40-C; cards 40-A wereeach impregnated with 12.5 g. DDVP; the other cards were eachimpregnated with 12.5 g. of a solution in DDVP of the followingcompounds at the following proportions:

40-B: 1% of bis(N,N-diethylthiocarbamoyl) disulphide 40-C: 2% ofbis(N,N-diethylthiocarbamoyl) disulphide This compound is commonlycalled tetraethylthiuramdisulphide.

The thus impregnated cards were suspended in a room, of which thetemperature was kept at 22:2" C. and of which the relative humidity wasabout 65.

At the end of 15 days the percentage quantity of DDVP destroyed weremeasured as given in Experiment 1 and tabulated as follows:

Card squares were used as described in Experiment 4. These cards weredivided into three series 41-A to 4l-C; cards 4l-A were each impregnatedwith 12.5 g. DDVP; the other cards were each impregnated with 12.5 g. ofa 1% solution in DDVP of one of the following compounds:

41-B: bis(N,N-dimethylthiocarbamoyl) sulphide 13 4l-Czbis(N,N-dimethylthi0carbamoyl) disulphide 14 The thus impregnated cardswere hung up in a room, the temperature of which was kept at 22i2 C. andthe relative humidity of which was about 40.

At the end of 15 days the percentage quantity of DDVP destroyed weremeasured as given in Experiment 1 and tabulated as follows:

ll-U EXPERIMENT 42 Doubled cards were used as described in Experiment 1but of weight 885 g./m. These cards were divided into seven series 42-Ato 42G. Cards 42A were each impregnated with 12.5 .g. DDVP; the otherdoubled cards were each impregnated with 12.5 g. of a 1% solution inDDVP of one of the following compounds:

42A 42-B 420 4.2-1) 42E 42F 42*G 34. 2 0 0. 03 0. 06 0. 06 0 O :lzO. 8:lzO :lzO. 01 i0. 01

The results of Experiments 40 to 42 show that the hydrolysis of thephosphoric ester such as DDVP can be reduced in substantial proportionwhich a thiuram compound of sulphur is added to the ester.

EXPERIMENT 43 Doubled cards were used as described in Experiment 1 butof weight 900 g./m. These doubled cards were divided into three series43-A to 43-0; the doubled cards 43 A were each impregnated with 12.5 g.DDVP; the other doubled cards were each impregnated 12.5 g. of a 1.5%solution in DDVP of one of the following compounds:

43-B: methylisothiocyanate 43-C: ethylisothiocyanate The thusimpregnated doubled cards were suspended in a room, the temperature ofwhich was kept at 22:2" C. and of which the relative humidity was about75.

i tlqgmpound commonly called tetramethylthiuram monosu p n e.

14 Compound commonly called tetramethylthiuram disulphide and knownunder the common name of thirame,

31 At the end of 15 days the percentage quantities of DDVP destroyedwere measured as given in Experiment 1 and tabulated as follows:

The results of this experiment show that the hydrolysis of thephosphoric ester such as DDVP can be reduced in substantial proportionswhen a sulphur compound selected from isothiocyanic esters is added tothe this ester.

EXPERIMENT 44 Card squares were used as described in Experiment 4 but ofweight 870 g./m. These cards were divided into five series 44-A to 44-E;cards 44-A were each impregnated with 17 g. DDVP; the other cards wereeach impregnated with 17 g. of a 1% solution in DDVP of one of thefollowing compounds:

44-B: thiourea 44-C: N,N'-dimethylthiourea 44-D: N,N'-diethylthiourea44-E: ethylene thiourea The thus impregnated cards were suspended in aroom, of which the temperature was kept at 20:2- C. and of which therelative humidity was between 55 and 60.

At the end of days, the percentage quantities of the DDVP destroyed weremeasured as given in Experiment 1 and tabulated as follows:

8. 7 :lzO. 4

EXPERIMENT 45 Card squares were used as described in Experiment but theweight of which was 885 g./m. These cards were divided into four series45-A to 45-D; cards 45-A were each impregnated with 17 g. DDVP; theother cards were each impregnated with 17 g. of a 1% solution in DDVP ofone of the following compounds:

45-13: N-methylthiourea 45-0: N-allylthiourea 45-D:N,N,N,N'-tetramethylthiourea 15 The thus impregnated cards weresuspended in a room, the temperature of which was kept at 22i2 C. andthe relative humidity of which was about 65.

At the end of 8 days the percentage quantities of DDVP destroyed weremeasured as given in Experiment 1 and tabulated as follows:

35. 3 3. 1 3. 4 21. 9 :l:2. 7 :lzO. 2 :i:0. 3 :|:1. 4

EXPERIMENT 46 Compound also known under the common name of thioslnamine.

32 At the end of 15 days, the percentage quantities of DDVP destroyedwere measured as given in Experiment 1 and tabulated as follows:

The results of Experiments 43 to 46 show that the hydrolysis of aphosphoric ester such as DDVP can be reduced in notable proportions whena sulphur compound chosen from thioureas is added to this ester.

EXPERIMENT 47 Doubled cards were used as described in Experiment 1 butof weight 880 g./m. These cards were divided into two series 47-A or47-B. Cards 47-A were each impregnated with 12.5 g. DDVP. The otherdoubled cards were each impregnated with 12.5 g. of a 2% solution ofDDVP of Z-methyl thiirane.

The thus impregnated cards were suspended in a room, the temperature ofwhich was kept at 20i2 C. and the relative humidity of which Was about60.

At the end of 10 days, the percentage quantities of DDVP destroyed weremeasured as given in Experiment 1 and tabulated as follows:

EXPERIMENT 48 Doubled cards were used as described in Experiment 1 butof Weight 895 g./m. These cards were divided into three series 48-A to48-C; the doubled cards 48-A were each impregnated with 12.5 g. of DDVP;the other doubled cards were each impregnated with 12.5 g. of a 1.5%solution in DDVP of one of the following compounds:

48-B: 2-ethyl thiirane 48-C: 2-chloromethy1 thiirane The thusimpregnated cards were suspended in a room, the temperature of which waskept at 22:2 C. and the relative humidity of which was about 70.

At the end of 15 days, the percentage quantities of DDVP destroyed weremeasured as given in Experiment 1 and tabulated as follows:

This experiment shows the particularly remarkable results which can beobtained in the stabilisation of phosphoric esters such as DDVP when asulphur compound chosen from thiiranes is added thereto.

EXPERIMENT 49 Doubled cards were used as described in Experiment 1 butof weight 900 g./m. These double cards are divided into four series 49-Ato 49-D; cards 49-A were each impregnated with 12.5 g. DDVP, the othercards being each impregnated with 12.5 g. of a solution in DDVP of oneof the following compounds at the concentration given:

49-B: 1.5 of N-triehloromethylthiophthalirnide 16 49C: 1.5% ofN-trichloromethylthiotetrahydrophthalimide The thus impregnated cardswere suspended in a room, the temperature of which was kept at 22i2 C.and the relative humidity of which was about 75.

Compound known under the common name of'fo1pet. Compound known under thecommon name of captane.

33 At the end of 15 days, the percentage quantities of DDVP destroyedwere measured as given in Experiment 1 and tabulated as follows:

The results of this Experiment show the hydrolysis of a phosphoric estersuch as DDVP can be reduced in notable proportion when a sulphurcompound chosen from sulphenamides is added thereto.

EXPERIMENT 5O 50B: 8-quinolyltrichloromethane su-lphanate 50C:4-methoxy-3-tertiobutylphenyltrichloromethane sulphenate 50 D:3,S-dimethoxyphenyltrichloromethane 'sulphenate The thus impregnatedcards were suspended in a room, the temperature of which was kept at22i2 C. and of which the relative humidity was about 75.

At the end of 10 days, the percentage quantities of DDVP destroyed weremeasured as given in Experiment 1 and tabulated as follows:

50-A EO-B 50-0 50D 36. 8 6. 6 l. 8 l. zit-0.

' The results of this experiment show that the hydrolysis of aphosphoric ester such as DDVP can be reduced in notable proportions whena sulphur compound selected from sulphenic esters is added to thisester.

EXPERIMENT 1 Doubled cards were used as described in Experiment 1 but ofweight 890 g./'m. These doubled cards were divided into two series Sl-Aand 51-B1 cards 51-A were each impregnated with 12.5 g. of DDVP; theother double cards were each impregnated with 12.5 g. of a 2% solutionin DDVP of 4,4'-dime=thoxythiobenzophenone.

The thus impregnated cards were suspended in a room, the temperature ofwhich was kept at 221-2" C. and the relative humidity of which was about70.

At the end of 15 days, the percent-age quantities of DDVP destroyed weremeasured as given in Experiment 1 and tabulated as follows:

51-A 51-B 41.1 3.0 i0.8 10.7

The results of this Experiment show that the hydrolysis of a phosphoricester such as DDVP can be reduced in substantial proportion when asulphur compound chosen from thi'o ketones is added thereto.

EXPERIMENT 5 2 Cards of size 5 x 10 cm. were used as described inExperiment 1 but left at a single thickness. These cards were dividedinto three series 52-A 'to 52-C. Cards 52A were each impregnated with 6g. of O(2.2-dibro movinyl) 0,0-dimethyl-phosphate. The other cards wereeach impregnated with 6 g. of a solution of one of the followingcompounds at 2% in O(2,2-dibromovinyl)0,0-dimethyl phosphate:

52-Bz 2(cyclohexylaminothio) benzothiazole 52-C2 zincN,N-d'iethyldithiocarb amate The thus impregnated cards were suspendedin a room, the temperature of which was kept at 22i2 C. and the relativehumidity of which was about 60.

At the end of 16 days, the percentage quantities of ester destroyed weremeasured poten'tiometrically. Account was taken of the starting aciditypresent in the phosphoric ester (equivalent to 7.4% of the ester) andthis was deducted from the results.

52-A 52-B 52-C 14.8 8.0 2.8

EXPERIMENT 5 3 53B: 2(cyc1ohexylaminothi-o) benzothiazole 53-C: zineN,N-diethyldithio carbam ate 53-D: bis (Z-benzothiazolyl) disulphide53E: bis(N,N-dimethylthiocarbamoyl) disulphide The thus impregnatedcards were suspended in a room, the temperature of which was kept at2212" C. and the relative humidity of which was about 60.

At the end of 48 days, the percentage quantities of DDVP destroyed weremeasured as given in Experiment 1 and tabulated as follows:

53-A 53-B 53-C 53 D 7.1 2.5 0 2.7

EXPERIMENT 54 Doubled cards were used as described in Experiment 1 butof weight 885 g./ m. These cards were divided into four series 54-A to54-D. Cards 54-A were each impregnated with 14 g. DDVP. The other doublecards were each impregnated with 14 g. of a solution in DDVP of one ofthe following compounds:

54-B: 1% of 2['(4-thiazoly1) methyl] benzimidazole 54-C: 1% ofazobenzene 54-D: 0.5% of 2[(4-thiazolyl) methyl]benzimidazole +05% ofazobenzene The thus impregnated cards were suspended in a room, thetemperature of which was kept at 2212 C. and the relative humidity ofwhich was about 65.

At the end of 12 days. the percentage quantities of DDVP destroyed weremeasured as given in Experiment 1 and tabulated as follows:

54-A 54-B 54-C 46.5 10.7 19.1

EXPERIMENT 55 Doubled cards were used as described in Experiment 1.These doubled cards were divided into five series 55-A to 55-E. Cards55A were each impregnated with 12.5 g. DDVP; the other cards were eachimpregnated with 12.5 g. of a solution in DDVP as follows:

55-B: 1% of thioacetamide 55-C: 1% of azobenzene 55D: 0.33%thioacetamide+0.66% azobenzene 55 E: 0.5% thioacetamide+0.5% azobenzeneAfter impregnation the double cards were each placed in a sachet formedby a mesh of nylon 66 made from 0.14 mm. thread and formed into a 0.3mm. mesh made by the French company Tripette et Renaud. The devices thusprepared were suspended in a room, the temperature of which was kept at22i2 C., and the relative humidity of which was about 40. At the end of15 days, the percentage quantities of the DDVP destroyed were measuredas given in Experiment 1 and tabulated as follows:

55-A 55B 55-C 65-D 55-E 38. 1 0. 6 3. 5 0. 15 i0. 6 :0. 1 :H). 8 i0. 02'

EXPERIMENT 56 Doubled in sachet cards were used as described inExperiment 55. The doubled cards were divided into six series 56-A to56-F. The cards 56-A were each impregnated with 12.5 g. DDVP; the otherdoubled cards were each impregnated with 12.5 g. of a solution in DDVPas follows:

56-B: 1% of 2-mercaptobenzothiazole 56-C: 1% of 4-diethylaminoazobenzene56-D: 0.5% of Z-mercaptobenzothiazole-l-0.5%

4-diethylaminoazobenzene 56-E: 1% of l-phenylazo-Z-naphthol 56-F: 0.5%of 2-mercaptobenzothiazole+0.5%

4-diethylarninoazobenzene The thus impregnated cards were suspended in aroom, the temperature of which was kept at 212 C. and the relativehumidity of which was about 35.

At the end of 30 days, the percentage quantities of DDVP destroyed weremeasured as given in Experiment 1 and tabulated as follows:

n6-A 56-13 56-C 56-D 56-E 56-F 44. 6 4. 5 3. 6 3. 6 12. 9 3. 8 :|:1. 0:tO. 4 :|:0. 5 :l:0. 5 :l:2. 0 :l:0. 4

EXPERIMENT 57 Doubled cards in sachets were used as described inExperiment 55 but in which the weight of the card was 900 g./m. Thedouble cards were divided into eight series 57-A to 57-H; cards 57-Awere each impregnated with 12.5 g. DDVP; the other double cards wereeach impregnated with 12.5 g. of a solution in DDVP as follows:

The thus impregnated cards were suspended in a room, the temperature ofwhich was kept at 22i2 C. and the relative humidity of which was about 70.

At the end of 30 days, the percentage quantities of DDVP destroyed weremeasured as given in Experiment 1 and tabulated as follows:

fi'l-A 57-B 57-0 57D 57-E 57-F 57-G 57-11 35. 1 0. 9 8. 4 0. 3 1. 1 (1.6 0. 7 0. 4 3:3 8 :izl). 1 ':l:2. 1 :bO. 07 :1:0. 3 3:0. 2 :lzO. 15:l:0. 07

The results of Experiments 54 to 57 show the value provided by mixturesof stabilisers according to the invention with stabilisers belonging tothe family of azoic compounds. There is in effect a synergistic effectusing these two types of stabilisers as shown by the results of theseExperiments.

EXPERIMENT 58 Double cards were used as described in Experiment 1 but ofweight 870 g./m. These doubled cards were divided into six series 58-Ato 58-F. Cards 58-A were each impregnated with 12.5 g. DDVP; the otherdoubled cards were each impregnated with 12.5 g. of a 1% solution inDDVP of one of the following compounds:

58-B: dibenzylsulphoxide 58C: dibutylsulphoxide 5 8-D 1,3-propanesultoneSS-E: diethyl-4-nitrophenylphosphorothionate 5 8-F:0,0-dimethyl-1,2,S+bis(ethoxycarbonyl) ethyl phosphorodithioate The thusimpregnated cards were suspended in a room, the temperature of which waskept at 22:2" C. and of which the relative humidity of which was about40.

At the end of 15 days, the percentage quantities of DDVP destroyed weremeasured as given in Experiment 1 and tabulated as follows:

58A 58 B 58-C 58-D 58-13 58-F 31. 6 31. 0 28. 8 33. 3 29. 6 31. 5 :lz2.4 :l:2. 0 :l .0. 6 5:1. 0 :l:1. 6 3:2. 2

EXPERIMENT 59 Doubled cards were used as described in Experiment 1 butof weight 895 g./m. These double cards were divided into four series59-A to 59D; cards 59-A were each impregnated with 12.5 g. DDVP; theother double cards were each impregnated with 12.5 g. of a 1.5% solutionin DDVP of one of the following compounds:

59-B: tetramethylene sulfone 59-C: diphenyl sulfone 59-D: paratoluenesulfonic acid The thus impregnated cards were suspended in a room, thetemperature of which was kept at 22:2" C. and of which the relativehumidity was about 70.

At the end of 15 days, the percentage quantities of DDVP destroyed weremeasured as given in Expermient 1 and tabulated as follows:

59-A 59B 69-C 59-D 36. 8 41. O 36. 1 42. 9 3:3. 9 i1. 0 :l:2. 0 :|:2. 1

The results of Experiments 58 and 59 show that it is not possible tostabilise a phosphoric ester such as DDVP with a sulphur compounddifferent from those defined and recommended by the present invention.

Several formulations are described below with the object illustratingthe invention but not of limiting it. For simplicity of expression, thesulphur compounds used are denoted as follows:

Compound A: Z-mercaptobenzothiazole Compound B: zinc salt ofZ-mercaptobenzothiazole Compound C: bis(N,N-dimethylthioearbamoyl)sulphide Compound D: bis(N,N-dimethylthiocarbamoyl) disulphide CompoundE: thioacetamide Compound F: zine N,N-dimethyldithiocar-bamate CompoundG: di-Z-benzothiazolyl disulphide Compound H: methylN,N-diethyldithiocarbamate Compound I: 1,3,5-trithiane The azoiccompounds used in several cases as complementary stabilisers are denotedas follows, with the exception of azobenzene which is designated by itsname:

Diazo compound A: 1-(4-phenylazophenylazo) 2-ethylaminonaphthalene Diazocompound B: 1-(3-methyl-2-nitrophenylazo) 3-ethoxycarbonyl-4,4-dimethyl-2 ,6-dioxo cyclohexane EXAMPLES 1 TO 10Insecticidal compositions comprising DDVP as phos- Z-naphphoric esterand at least one divalent sulphur compound as principal stabiliser forthis ester, these compositions also optionally containing a solvent forthe ester and/or complementary stabiliser selected from azoic compoundsand epoxidised compounds. Values in the following table and in thetables appended to the remainder of these examples are in parts byWeight.

TABLE I Example DDVP 98. 8 98 99. 3 75 70 78 65 85 90 50 Dioctylphthalate 20 20 45 Dibutyl sebacate.- 20 9.2 Diiso octyl adipate 33 1OAzobenzene 0. 5 0.2 Diazene D Diazene E 0.4

Soya oil 4.5 Octy] epoxystearate 0.8

Compound A Compound D 1. 2 Compound G Compound H 0.8

EXAMPLES 11 TO 20 Insecticidal composition comprising DDVP as phosphoricester at least one divalent sulphur compound as principal stabilisertherefor, a Vaseline or paraflin oil as solvent, a heavy alkanone asco-solvent and in some cases a complementary stabiliser selected fromazoic and epoxidised compounds.

TABLE II-Continued Example Laurone 13 9. 9 6 12 Palmitone. 10 IOStearone... 12.4 12.4 12.5

Cyclohexyl epoxystearate 1 Epoxidised soya oil 1. 8

Diazene B 0. 1 0.1 0. 1 Diazene C 2 1 Diazene D 0.5

Com ound C 1 2 0.1 2 1 1.5 Compound E 1 0. 4 Compound F 0.5 0.2 0.8

i Semi-refined oil having a density of 0.867 at 15 C. and a gelationpoint of about 42 C.

Semi-refined oil having a density of 0.370 at 15 C. and a viscosity of107 Engler at 50 C.

EXAMPLES 21 TO 30 TABLE 111 Example DDVP 15 18 16 20 33 27 28 33 20 20Ordinary paraiiin:

52/51)". 65 Vaseline 32 3a 30 Petrolaturn Laurone 19 23 23 24 24 24Stearone 33 37 36 32 Epichlorohydrine 3.5 1 2.5

DiazeneD 0.2 0.5 0.5 Azobenzene 0.4

Compound 13 0.4 0.2 0.3 Compound D. Compound G" Compound. I 0. 5 1 0. 5tli Commercial product of yellow colour having a dropping point greaterran 47) i Chestnut coloured product having a dropping point of about 720.

Examples 31 to Insecticidal compositions usable in a wick evaporatorformed by a reservoir and a Wick dipping into the composition and havinga part exposed to the free air. These compositions comprise DDVP asphosphoric ester, a sol- TABLE H E m 1 vent from the ester chosen fromamong alkanes, a com p e solvent selected from chlorodecane,3,6,9-trioxaundecane, 11 12 13 14 15 16 17 18 19 and5,8,11trioxapentadecane, at least one divalant sul- DDVP 50 25 40 40 55phur compound as principal stabiliser for the phosphoric Vasefine oil 354s 4s 36 36.5 ester and in some cases a complementary stabiliser se-Parafiin oil 36.7 m. 3 17 60 37 lected from azoic and epoxldisedcompounds.

TABLE IV Example DDVP 9.2 8.5 8.5 9.2 9.2 10.6 10.6 9.7 9.7 7.8

n-Dodecane 1 85.2 85.9 IsoparL 86 87.4 80.7

l-chloro decane 3,6,9-trioxaundecane 5,8,ll-trioxapentadecanc Epoxidisedsoya oil Diazaene A- Compound H.

k Co-solvent known under the name of diglycol diethyl ether andmanufactured under the trademark Diethylcarbitol by the United StatesCompany Union Carbide Chemicals 00.01 New York.

Co-solvent known under the name of diglycol dibutyl ether sold under thetrademark Dibutylcarbitol by the Union Carbide Chemicals Co.aforementioned.

Distillation out between 189 and 205 C. of aliphatic branched chainhydrocarbons obtained by synthesis containing a mixture of decane,undecane and dodecane, produced by the company Esso Standard.

39 Examples 41 to 50 Insecticidal compositions comprising DDVP asphosphoric ester, at least one divalant sulphur compound as principalstabiliser for this ester, an odorant material selected from linalol,ionone, methone, linalyl acetate, orange terpenes, and citron terpenesand in some cases a complementary stabiliser selected from azoic andepoxidised compounds.

TAB LE V Example DDVP 79.3 65 79.3 79.5 89 83 Linalol Alpha ionone.Menthone- Li nalyl acetate. Orange terpenes. Citron terpones Epoxldisedsoya oil...

Diazaene A Diazaent B Compound A Compound C Compound G- Compound H.

Examples 51 to 60 Insecticidal compositions comprising DDVP asphosphoric ester, at least one divalant sulphur compound as principalstabiliser, a synthetic thermoplastics resin as solid solvent, and aheavy ester used as co-solvent at the same time as in some cases as aplasticiser for the resin and in some cases a complementary stabiliserselected from azoic and epoxidised compounds:

TABLE VI Example DDVP Polyvinyl chloride Ethylene/vinylacetate copolymerm Vinyl acetate vinyl chloride copolymer (10:90)

Diiso octyl adipate. 23 9 Tricrosyl phosphate 10 29 12 19 5 Methyllaurate 5 9 Dioctyl phthalate 9 8 Dimethyl succinate l5 9 Dimethylmaleate l0 10 Octylcpoxystearate 2 1 Epichlorohydrine 0.5

Diazene C 0.6 0.2 0.8 DiazeneD 0.5

Coloured pigments 0.5 0.5 0.4

Compound B 0.2 Compound C. Compound D Compound G 0.5 1.8

m Copolymer of 67% ethylene of 33% vinyl acetate having an intrinsicviscosity of 0.78 for 0.25 g. in 100 ml. toluene at 30 C.

Product sold under the trademark Blue Irgalith BL" and defined in thecolour index under N 0. 74100 (pigment blue 15).

Examples 61 to 70 Insecticidal compositions comprising DDVP asphosphoric ester, at least one divalent sulphur compound as principalstabiliser for this ester, a paratfin as solid adjuvant, a fossil silicaas mineral adjuvant and in some cases a complementary stabiliserselected from azoic and epoxidised compounds, a copolymer of ethyleneand vinyl acetate as an agent improving the mechanical properties of theparaffin, a pigment and/or a modified montmorillonite as dispersingagent permitting the homogeneity of the composition to be maintainedbefore cooling.

TABLE VII Example DDVP 23 25 25 25 24 24. 5 24. 5 24. 5 24. 25 24. 25

Ordinary paraflin 60/62 60 57 46 46 54 54 58 58. 5 65.5 65. 5

Copolymer of ethylene and vinyl acetate (71:29) 12 12 Fossil diatoms 1516 15 15 15 15 15 15 Amine oleate 5 5 Modified Inontmon'llonite 1 1 9. 09.

Pigment 1. 0 0. 8 0. 5 0. 6 0. 5

Epoxidised soya oil .4; 0.5 O. 7 Cyclohexyl epoxystearate 0. 9

Azobenzene 0.5 0. 5 Diazene B 0. 4

Compound A Compound B Compound D Compound F Product sold under the markYellow Irgalith BAW and defined in the colour index under the no.21100(pigment yellow l3).

Product arising from the reaction in molecular ratio of 2:1 betweenoleic acid and a mixture of the following diamines:hexadecylaminopropylene amine (10%); octadecylaminopropylene amine (5%);octadecylaminopropylene amine H A mixture of dimethyldihexadecylammonium montmorillonite (70%) and dimethyldioctadecylammonium montmorillonite.

